Insights into the Reactivity of 2-Hydroxycyclobutanones with Thiols Corroborated by Quantum Chemical DFT Investigations and NMR and Raman Analysis

Abstract

A general strategy for the synthesis of 2-substituted cyclobutanone sulfides via a tandem Brønsted acid-catalyzed nucleophile addition/ring contraction/C3-C4 ring expansion reaction sequence has been exploited. The procedure led to a wide panel of four-membered cyclic ketones in good to excellent yields and with broad substrate scope. Mechanistic aspects and kinetic parameters were investigated by quantum chemical DFT calculations, allowing us to rationalize the different reactivity of 2-aryl- and 2-alkyl-substituted 2-hydroxycyclobutanones towards thiol nucleophiles in reactions mediated by sulfonic acids. NMR and in situ Raman techniques were employed to better understand the reaction kinetics and parameters that affect the desired outcome.

Key words

cyclobutanones - thiols - ring contraction - ring expansion - Brønsted acid catalysis - transposition - quantum chemical DFT

Publikationsverlauf

Eingereicht: 30. Juni 2022

Angenommen nach Revision: 28. Juli 2022

Accepted Manuscript online:
28. Juli 2022

Artikel online veröffentlicht:
10. Oktober 2022

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